Synthesis, Structure, and Catalytic Properties of Palladium(II) bis(diphenylcyclohexylphosphine) (η5-cyclopentadienyl) Tetrafluoroborate in Butadiene Telomerization with Methanol

A new cationic palladium complex [Pd(η 5 -C 5 H 5 )(PPh 2 Cy) 2 ]BF 4 ( I ) is prepared by the reaction of [Pd(acac)(PCyPh 2 ) 2 ]BF 4 with cyclopentadiene in the presence of BF 3 ·OEt 2 . The structure of complex I is determined by XRD. Results of the DFT studies at the BP86-D3/def2-TZVP level of theory along with QTAIM and NOCV methods suggest that the hapticity of the cyclopentadienyl ligand in I adopts an intermediate type of coordination between η 3 and η 5 . Compound I demonstrates a catalytic activity in the reaction of 1,3-butadiene telomerization with methanol with a catalyst turnover number up to 43100 (mol·BD)/(mol·Pd) for 6 h and a 76% selectivity to telomeres.